Alvarez M Angeles, García M Esther, García-Vivó Daniel, Ruiz Miguel A, Toyos Adrián
Departamento de Química Orgánica e Inorgánica/IUQOEM, Universidad de Oviedo , E-33071 Oviedo, Spain.
Inorg Chem. 2015 Nov 16;54(22):10536-8. doi: 10.1021/acs.inorgchem.5b02292. Epub 2015 Nov 3.
Complex [Mo2Cp2(μ-PCy2)(μ-NO)(NO)2] (1) was prepared by reacting [Mo2Cp2(μ-H)(μ-PCy2)(CO)4] with 2 equiv of [NO]BF4 and then treating the resulting product Mo2Cp2(μ-PCy2)(CO)2(NO)2 with NaNO2 at 323 K, and it was shown to display a bridging nitrosyl ligand with significant pyramidalization at the N atom, a circumstance related to an unusual behavior concerning degradation of the bridging nitrosyl. Indeed, complex 1 reacts with HBF4·OEt2 to give the nitroxyl-bridged derivative Mo2Cp2(μ-PCy2)(μ-κ(1):η(2)-HNO)(NO)2, is reduced by Zn(Hg) in the presence of trace H2O to give the amido complex [Mo2Cp2(μ-PCy2)(μ-NH2)(NO)2], and reacts with excess P(OPh)3 to give the phosphoraniminato-bridged derivative [Mo2Cp2(μ-PCy2){μ-NP(OPh)3}(NO)2].
通过使[Mo2Cp2(μ-H)(μ-PCy2)(CO)4]与2当量的[NO]BF4反应，然后在323 K下用NaNO2处理所得产物Mo2Cp2(μ-PCy2)(CO)2(NO)2，制备了配合物[Mo2Cp2(μ-PCy2)(μ-NO)(NO)2] (1)，结果表明其显示出一个桥连亚硝酰基配体，该配体的N原子具有显著的锥体化，这种情况与桥连亚硝酰基的异常降解行为有关。实际上，配合物1与HBF4·OEt2反应生成硝酰基桥连衍生物Mo2Cp2(μ-PCy2)(μ-κ(1):η(2)-HNO)(NO)2，在痕量H2O存在下被Zn(Hg)还原生成氨基配合物[Mo2Cp2(μ-PCy2)(μ-NH2)(NO)2]，并与过量的P(OPh)3反应生成磷亚胺基桥连衍生物[Mo2Cp2(μ-PCy2){μ-NP(OPh)3}(NO)2]。
